DE2060198A1 - Pyrazolo- (thiono) -phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU SE N-Beyerwerk P «ent department Hu / MBp '/, l, \ Z-

Pyrazolo (thiono) phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides

The present invention relates to new pyrazolo (thiono) phosphorus (phosphonic) acid esters, which have insecticidal and acaricidal, sometimes rodenticidal and fungicidal properties and a process for their manufacture.

From the USA patent specification 2 754 244 it is already known that methylpyrazolo (thiono) phosphoric acid ester, ζ. Β. the 0,0-Mmethyl- or 0,0-diethyl-0- / 5-methylpyrazol (3) yl7-thionophosphoric acid ester, have an insecticidal and acaricidal effect.

It has now been found that the new pyrazolo (thiono) phosphorus (phosphonic) acid esters of formula (I)

CN OR ₉

^R 1

in which

R and R ^ stand for identical or different, straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, .R ₁ also an alkoxy with 1 to 6 and

Et and R ^ each represent an alkyl radical with 1 to 4

Represents carbon atoms and Y represents an oxygen or sulfur atom,

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have strong insecticidal and acaricidal, sometimes rodenticidal and fungicidal properties.

It was also found that the pyrazolo (thiono) phosphorus = (Phosphonic) acid esters of the constitution (I) can be obtained by using (thiono) phosphorus (phosphonic) acid ester halides of formula (II)

RO Y

P-HaI (II)

with 1-alkyl-3-hydroxy-4-cyano-5-alkyloxypyrazoles der Structure (III)

HO. CN

in the form of the corresponding salts or in the presence of acid binders implemented, where in the aforementioned formulas R, R- ,, Rg. R and Y have the meaning given above, while Hai stands for a halogen, preferably chlorine, atom.

Surprisingly, the pyrazolo (thiono) phosphorus (phosphonic) acid esters according to the invention are characterized by a significantly better insecticides

and acaricidal effect on the known methylpyrazolo (thiono) phosphoric acid esters analogous constitution and the same direction of action. The compounds according to the invention thus represent a real asset to technology.

If one uses, for example, 0,0-diethylthionophosphoric acid = diester chloride and 1-methyl-3-hydroxy-4-cyano-5-ethoxypyrazole

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as starting materials, the course of the reaction can be through the following equation is given:

S acid bins- S

(C ₂ H ₅ O) ₂ P-Cl + HC) ON ( ^c _? H _? 0) ₉ P-0

CH, ₅

The starting materials to be used for the manufacturing process are generally clearly defined by the formulas (II) and (III). In formula (II), however, R and R ₁ preferably represent straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sea- or tert-butyl, R - also preferably denotes an alkoxy group with 1 to 4 carbon atoms, and R ₂ and R preferably represent methyl, ethyl, propyl and iso-propyl.

As examples of (thiono) -phosphorus (phosphonic) acid ester halides to be used according to the process (II) are mentioned in detail:

0,0-diicethyl-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-di-isopropyl-, O, O-dibutyl-, O, O-di-tert-butyl-, 0-methyl-O-ethyl-, 0-methyl-O-propyl-, 0-methyl-O-iso-propyl-, 0-methyl-O-butyl-, 0-ethyl-O-propyl-, 0-ethyl-O-iso-propyl-, 0-ethyl-O-butyl-, O-propyl-O-iso-propyl-, O-butyl-0-tert-butyl-phosphoric acid = ester chloride or the corresponding thiono analogs, furthermore 0-methyl-methane, 0-ethyl-propane, 0-iso-propyl-ethane, O-butyl-methane, O-ethyl-methane, Q-ethyl-butane, 0-iso-propyl-methane-phosphonic acid ester chloride and the corresponding thiono compounds.

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The (thiono) phosphorus (phosphonic) acid ester halides required as starting materials of constitution (II) are known from the literature and are also easy on an industrial scale accessible.

The pyrazole derivatives of constitution (III) can by a method not belonging to the prior art, for. B. off Connections of the following type

CH, OC SCH,
3/3

C = C
NC ^X O alkyl

and monalkylhydrazine can be obtained.

The manufacturing process for the new substances (i) is preferred carried out with the use of suitable solvents or diluents. As such, practically all inert ones come organic solvents in embossing. This includes especially aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene = chloride, chloroform, carbon tetrachloride, chlorobenzene, ether, e.g. B. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as aceto and propio = nitrile.

All customary acid binders can be used as acid acceptors. Alkali = have proven particularly useful carbonates and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

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The reaction temperature can be varied within a relatively wide range. In general, one works between 0 and 120, preferably at JO to 40 ^{0 0} .

The reaction is generally carried out at normal pressure. leads.

The starting materials are used to carry out the process mostly in equimolar proportions. An excess of the one or the other reaction component brings no significant advantages. The reaction is preferred in the presence carried out one of the abovementioned solvents and in the presence of an acid acceptor at the temperatures indicated. After several hours of stirring - if necessary with heating - the reaction mixture is poured into water, with a hydrocarbon, preferably benzene, added and worked up by customary methods.

The products according to the invention are mostly obtained in the form of colorless to slightly yellow colored, viscous, water-insoluble oils, which cannot be distilled without decomposition, but by so-called "partial distillation", d. H. prolonged heating under reduced Pressure to moderately elevated temperatures, freed from the last volatile components and cleaned in this way can. The Brephungsindex is primarily used to characterize them. However, if the compounds are obtained in crystalline form Shape, they are characterized by their melting point.

As already mentioned several times, the new pyrazolo (thiono) phosphorus (phosphonic) acid esters stand out due to its excellent insecticidal and acaricidal effectiveness against plant, Hygiene and storage pests. You own both a good effect against sucking as well as eating insects and mites (acarina). At the same time, they have a low

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Phytotoxicity and partly rodenticidal and fungicidal properties. Therefore, the products according to the invention as a pesticide, especially in the plant and stored product protection as well as in the hygiene sector.

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The sucking insects essentially include klattlause (Aphidae) such as the green peach leaf claus (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato louse (Macrosiphum solanifolii), also the currant gall (Gryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus eerasi), außardem scale and mealybugs (Coccina), e.g. the Ivy shield (Aspidiotus hederae) and cup scale (lecaniuia hesperidum) and the mealybug (Pseudococcus maritimus); Bladder feet (Ihysanoptera) such as Hercinothrips femoralis and bed bugs, for example the beet (Piesma quadrata), cotton (Dysdercus iatermedius), bed bug (Gimex lectularius), predatory bug (Rhodniua prolixus) and Chagas bug (Triatoma infestans), furthermore Cicadas, such as Euscelis bilobatus and Uephotettix bipunctatus.

Among the biting insects, butterfly caterpillars should be mentioned above all (lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden afters (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small cheetahs (Cheimatobia brumata), oak curlers (Tortrix viridana), the Army (Iaphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones Wax moth (Galleria mellonella),

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The biting insects also include beetles (Coleoptera), for example corn (Sitophilus granarius = Galandra granaria), potato (leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), raspberry (Meligethes aeneus), raspberry - (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common meal beetle (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground ζ.B * wireworms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches such as the German (ßlattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae, oriental (Blatta orientalis), giant (Blaberus giganteus) and black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; furthermore, Orthopterenia the cricket (Acheta domesticus); termites such as the terrestrial termites (Reticulitermes flavipes) and hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Pannia canicularis), Glossy fly (Phormia aegina) and blowfly (Calliphora erythrocephala) as well as the calf trigger (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles Stephens!).

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The mites (Acari) include especially the spider mites (Tetranychidae) such as the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ul-. ni), gall mites, e.g. the currant gall mite (Eriophyes ribis) and tarsonemids, e.g. the shoot tip mite (Hemitarnonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata),

When used against hygiene and storage pests, special »flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed Documents from.

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Depending on their intended use, the new active ingredients can be added to the Conventional formulations are transferred, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers, optionally with the use of surface-active substances Agents that are emulsifying and / or dispersing agents, e.g. in the case of using water as an extender organic solvents can optionally be used as auxiliary solvents. As a liquid solvent are essentially possible: aromatics (e.g. xylene, Benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; as solid carriers: natural Rocks (e.g. kaolins, clays, talc, chalk) and synthetic rock flour (e.g. highly dispersed silica, Silicates); as emulsifiers: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkyl aryl polyglycol ethers, alkyl sulfonates, and aryl sulfonates; as a dispersant: e.g. lignin, Sulphite liquors and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

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The formulations generally contain between 0.1 urd 95 percent by weight active ingredient, preferably between 0.5 and 90 96.

The active ingredients can be used as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, narcotics and granules can be used. It is used in the usual way, e.g. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying., Pouring, Pickling or encrusting.

The ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10 %, preferably between 0.01 and 1 % »

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100% active ingredient alone.

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Example A.
Plutella test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of active compound and they are populated with caterpillars Cabbage moth (Plutella maculipennis).

After the specified times, the degree of destruction is determined in % . 100% means that all caterpillars were killed, while $ 0 indicates that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 1 below:

Active ingredient

$ 1

Table 1

(Plutella test)

Acts off concentra ion in jo

Degree of destruction

in jo after 3 days

₂₅₂

(known)

₅₂

(known)

OH,

0.1 0.01

0.1

100 O

ο ClT UAcH - 13 0 , 01 100 (CH ₃ O) Il SI
Il
₂ P-0> ^ OCH ^ 209825/11 0 ,1 90 J I ■ ^ N ^ CH ₃ 0 , 01 100 (C ₂ H ₅ O) ^ OCH ₃ 0 ,1
, 01 100 C ₉ HcO CN ^ Ν ^ _Η 0
0 , 001 100
100 U ₂ M ₅ s ι
mi I
PO ^ ' 3 0 ,1 55 CN ^ OCH ^ 0 , 01
, 001
, 0001 100 CH,
1-C ₃ H ₇ O ' S "Ί
Il J
, PO - "^ ¹ ^ N ^ CH ₃ 0
0
0 ,1 100
100
50 376 OC ₂ H ₅ 0 , 01 100 (CH ₃ O), ^ N " ^N ^ CH ₃ 0 100 Le A 13 AA

Port setting Table 1

(Plutella test)

Active ingredient active ingredient concentration degree of destruction in </ o in ° / o after 3 days

CN ___ ^ OC ₂ H ₅ 0.1 100

χ »ii ° ^{'01 10} °

(C ₂ H ₅ O) ₂ P-OA _n AcH _{3 OfOO1 70}

C N OC ₉ H ₅ 0.1 100

^C 2 ^H 5 ° \ ^ I i 0.01 100

/ ^{υ ίΛ u ± 1} 3 0.001 100

^G 2 ^H 5 0.0001 90

o, 1 100

C N OC _? H ₇ -i 0.1 100

0.001 100

° ^{001 80}

^0CH 3 0.1 100

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2. Continuation

Table 1·

(Plutella test)

Active ingredient C ^ OC ₂ H ₅ Active ingredient concentrations
entered ion in / 0 Degree of destruction
in fo after 3 days υ ι -
(C ₂ H ₅ O) ₂ PO An. - ¹ ^ CH ₃
0C, H ₇ 0.1 100 u ι -
(C ₂ HcO) ₂ PO- ^ N- 3 0.01
0.001
-i 0.1
0.01
0.001 100
70
100 100
35

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Example B.

Myzus test (contact effect)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the production of an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amount of solvent which contains the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.

The preparation of the active compound is used to produce cabbage plants (Brassica oleracea), which are strongly influenced by the peach aphid (Myzus persicae) are infected, sprayed dripping wet.

After the specified times, the degree of destruction is determined in $. 100 $ £ means that all aphids have been killed, 0 ^c ß> means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, processing times and results are shown in Table 2 below:

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Tabel

(Myzus-Teat)

Active ingredient CN C ₂ H ₅ ^ ^ CH ₅ Active ingredient concentrations
tration in fo - 17 - Degree of destruction
in fo after 1 day S. (CH ₅ O) ₂ PO- CH, S ^ l
3n, i I 0.1 825/1 U4 100 dd
(GpHcO) pP-0- S ^ l
(C ₂ H ₅ O) ₂ PO- ¹ XC ₅ H ₇ O 0.01 30th (known) CN CN
■ 5 1
(CH ₅ O) ₂ PO- * S. Ie A 13 376 0.1 0 (known) ^ OCH ^ 0.1 100 ^ OCH ₅ 0.01
0.001 1 00
100 3 0.1
0.01
0.001 100 _0CH ^ 0.1 100
100 Ui-CH ₅ 0.01
0.001 100 0.0001 100
100 ^ OCH ₇ ; 0.1
0.01 70 0.001 100 ³ 0.1
0.01
0.001 ■. 100 _r ⁰⁰ 2 ^H 5
3 99 100
100
98 20 9

20BÜ198

Port setting

Tabel

Active ingredient

(Myzus test)

tration in

nzen- Degree of destruction
in ^c / o after 1 day 0.1 100 0.01 98 0.001 90 0.1 100 0.01 100 0.001 98 0.0001 95 0.1 100 0.01 100 0.001 100 0.0001 90 0.1 100 0.01 100 0.001 98 0.0001 70 0.1 100 0.01 100 0.001 100 0.0001 100 0.1 100 0.01 100 0.001 99

CN

(C ₂ H ₅ O) ₂ PO- ^ N

CN

.0C ₂ H ₅

> CH,

OC ₂ H ₅

C ₂ H ₅ OST = T

PO- ^ N- ¹ MJH,

C ₂ H ₅

11

(CH ₃ O) ₂ PO

(C ₂ H ₅ O) ₂ P-0

2 5 "

P-O

CH ₃ S /

OC ₃ H ₇ -I

OC ₃ H ₇ -I

OC ₃ H ₇

OC ₃ H ₇ -X

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13th

2. Port setting

Tabel

Active ingredient

(Myzus test) Degree of loss Act ο ffkonz en- in f> after 1 day tration in fo 100 0.1 100 0.01 85 0.001 100 5 0.1 100 0.01 95 0.001 50 0.0001 100 ₇ -i 0.1 100 0.01 99 0.001

O ^ T =

(C ₀ HcO) ₀ P-

CN OC

o V = ^

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Example C
Tetranychus test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Bean plants (Phaseolus vulgaris), which are about 10-30 cm high, dripping wet sprayed. These bean plants are strong with all stages of development of the genius spider mite (Tetranychus urticae) infested.

After the specified times, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of death obtained is given in $. 100 i » means that all spider mites have been killed, 0 $ means that none of the spider mites have been killed.

Active ingredients, ingredient concentrations, evaluation times and The results are shown in Table 3 below:

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Tabel

(Tetranychus test)

206Q198

Active ingredient

Active ingredient concentration in </ o

Degree of destruction

in jo after 2 days

(C ₂ H ₅ O) ₂ PO (known)

s r =

ti

0.1

(CH ₃ O) ₂ PO (known)

0-,

CN

OCH

S T ^ =

(CH ₅ O) ₂ PO

Il

CN

(C ₂ H ₅ O) ₂ PO C

CN

OCH ^

i-0, H "0

Il

(C ₂ H ₅ O) ₂ PO ^ *

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3 0 , 01 0 ,1 3 0 , 01 0 ,1 ⁵ 0 , 01 0 ,1 3 0 , 01. 0 , 001 0 ,1 H 0 , 01 O ₁ - 21 - U 209825/11 '

100 60

100 99

100 90

100 100 100

100 60

Port setting Table 3

(Tetranychus test)

Active ingredient active ingredient concentration degree of destruction in ^ in <f> after 2 days

, OC ₂ H ₅

C ₀ H ^ OSP = T ^ ⁵ 0.1 100

^d ? \ » I.

0.01 99

C ₂ H ₅

^^ OC ₃ H ₇ -I 0.1 100

Ι ί 0.01 98

Cn χι η ¹ ) ρ η- ^ "w- ^
^ 2 5 2

C ^, OC ₃ H ₇ -I ₀

CH, S 1 Γ ^ ' '

0.001 70

0.1 100

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Example D

Mosquito larva test

Test animals Aedes aegypti larvae

Solvent: 99 parts by weight acetone Emulsifier: 1 part by weight of benzylhydroxydiphenyl =

polyglycol ether

For the production of a suitable active ingredient preparation dissolve 2 parts by weight of active ingredient in 1000 parts by volume of solvent, contains the emulsifier in the amount specified above. The solution thus obtained is adjusted to the desired with water diluted in lower concentrations.

Jian fills the aqueous active ingredient preparations into jars and then put about 25 mosquito larvae in each glass.

After 24 hours, the degree of destruction is determined in i ° . Here 100 ^ means that all larvae have been killed. Q $> means that no larvae have been killed at all.

Active ingredients, active ingredient concentrations, test animals and results can be seen from the following table 4:

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Tabel

(Mosquito larva test / Aedes aegypti)

Active ingredient

Active ingredient concentration of the solution in ppm

Degree of destruction in %

S N = C-CH,

Il / 3

> ^P - ^N _S

C-CH,

(known)

KJ

(CH ₃ O) ₂ PO- ^ P

CH,

N-NH

(known)

10

10

100

CN OCH

(CH, C

N-N-CH,

10 1 0.1

100

100

CN OCH

(C ₂ H ₅ O) ₂ PO ^

N-N-CH,

10 1 0.1

100

100

100

GN OCH,

P-O

10 1

0.1

100 10Q

1PP

IPQ

Lei 1

- 24 -

Ρίϋ * ■ ■ " ψ-i- -: ■ - " »■

Continuation . Table 4

(Mosquito larva test / Aedes aegypti)

Active ingredient Active ingredient concentrations
tration of the solution
in ppm Degree of destruction
in ψ S \ / 3 Ί '" ¹ IO 100 (CH ₃ O) ₂ PO -ζ \ 1 100 N-N-CH, 0.1 100 Pitt "ΛΠ ti
c, KjIY UO, Hr,
\ / -5 ι '~ ^X 10 100 (C ₂ H ₅ O) ₂ PO - / ^] 1 100 NN-CH ₃ 0.1 90 CoHr-O S ν / 3 7
2 5 \ "W /
/ - ⁰ St.
C ₂ H ₅ NN-CH ₃ 10
1
0.1 100
100
100 « _{H q} CN OCH,
C ₂ H ₅ O NN-CH ₃ 10
1
0.1 100
100
100 _{rTJ q} CN 00, H ₇
^GH 3 \ | ₀ _V | ^{5 7}
1-C ₃ H ₇ O ⁷ NN-CH ₃ -i
10
1 100 ',' CN. . OCoHr-
V / ^ 5 10 100 (G ₂ H ₅ O) ₂ P-0- / |. 1 100 NN-CH ₃ 0.1 70

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2. Continuation of Table 4

(Mosquito larva test / Aedes aegypti)

Active ingredient CN OC ₂ H ₅ Active ingredient concentrations
tration of the solution
in ppm Degree of destruction
in fo O ₂ H ₅ O _n S NN-CH ₃ 10 100 CN OCpH ₁ -
v ___ / - ^ 1 100 0 NN-CH ₃ 10 100 (C ₂ H ₅ O) ₂ PC 1 100

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■ if

Example E.

LT ₁₀₀ -Test for Diptera
Test animals: Aedes aegypti
Solvent: acetone

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution obtained in this way is diluted to the desired lower concentrations with further solvent. \

2.5 ml of the active ingredient solution are pipetted into a Petri dish. There is a filter paper on the bottom of the Petri dish with a diameter of about 9 »5 cm. The Petri dish remains open until the solvent has completely evaporated is. Depending on the concentration of the active ingredient solution, the

Amount of active ingredient per m of filter paper varies. Afterward about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is checked after 1, 2 and 3 hours. The time is determined which is necessary for 100% destruction. \

Test animals, active ingredients, active ingredient concentrations and times at which there is a 100 fii ge kill can be seen from the following table 5:

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Table 5

(LT ₁₀ Q-Te3t for Diptera / Aedes aegypti)

Active ingredient

Active ingredient concentration of the solution in io

LT

3 N

(C ₉ HcO) ₉ PN
2 5 2 γ

C-

■ = C-CH,

■ OH,

Il

(known)

It

N-NH

(known)

0.2 0.02

0.2

60 '120'

* =

GN OCH-:

Q ₂ H ₅ Q

-N-CH

CH, S <\ »/ ^0CH 3

i-σ, ΗαΟ

NN-OH ₃

GN

OF ν

0.2

0.02

0.002

0.2

0.02

0.002

0.2

0.02

0.002

0.2

Q »Q2

Q _f QQ2

6Q I. 60 I. = 60 60 t 60 I. 18Q I. 60 I. 60 I. 50 60 I. 60 I. 180 I.

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Continued from table 5

for Diptera / Aedes aegypti)

Active ingredient active ingredient concentration the solution

NN-CH 0.02
0.002

60 '180'

^C 2 ^H

0.2

0.02

0.002

60 '60 »60 ^f

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so

Example F

for dipteras

Test animals: Musca domestica

Solvent J acetone

2 parts by weight of active ingredient are dissolved in 1000 parts by volume recorded. The solution obtained in this way is adjusted to the desired lower concentrations with further solvent diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9 »5 cm. The petri dish remains Stand open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution

2
the amount of active ingredient per cm of filter paper varies.

Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which is necessary for a 1005 knock-down effect necessary is.

Test animals, active ingredients, active ingredient concentrations and times, who have a 100 / £ knock-down effect, leave from the following table 6:

Le A 13 376 - 30 -

209825/1 IU

Tabel

for Diptera / llusca domestica)

Active ingredient

Active ingredient concentration of the solution in fo LT

100

C-CH

Il

(known)

0.2 8 ^X

Il

(known)

(CH ₃ O) ₂ PO

Ή ^CH 3

QlI

0.2

0.2 0.02 0.002 0.0002 =:

80 '85'

60

-H-CH,

0.2 0.02 ■ 75 '240'

0.2

0.02

0.008 45 '11Q »

-N-CH,

0.2

0.02

0.002 85 '85'

le A 13 376

- 31 -

2Q9825 / 1U4

Continuation table

for Diptera / Musca domestica)

Active ingredient concentration-active ingredient tration of the solution ^LT 1OO

in

_n CN OCH, ° ' ^{2 60} '

" V- / ³ 0.02 100 '

(C ₂ H ₅ O) ₂ PO ^ "] _{0> 002 6} h

_M-CH3 0.0002 8 ^h = 60

S CN OC ₃ H ₇ -I _{0> 2 65} ,

(CH ₇ O) ₉ PO- (I 0.02 65 '

NN-CH, 0.002 8 ⁿ = 80

0.2 65 '

_{OfO2 220} ,

C ₂ H ₅ O _n S. CN ( 0 * 2 > -0 _ / | 0 i 02 C ₂ H ₅ N-N- 0 » 002 ) 0 ₃ H ₇ -CH ₃

i-C 3 ^H 7 ° . NN-CH ₃ 0 , 2 0 CN OC ₃ H ₇ -X 0 , 02 (C ₂ H ₅ O) ₂ 0 , 002 NN-CH _x

160

0.2 60 '

0.02 160 '

30 '45

8 ^h =

Le A 13 376 - 32 -

209825/1 UA

2. Continuation

Active ingredient

Tabel

for Diptera / Musca domestica)

Active ingredient concentration of the solution in yes

^G ^ y ^0G 2 ^H 5

C ₂ H ₅ OS

-N-GH

CN OC ₉ H
W ²

0.2

0.02

0.002

0.2

0.02

0.002

0.2

0.02

0.002

0.2 0.02 60 195

6 ^h 1 8 ^h 1 = 50 ok 35 25th 6 ^h = 90 io 40 fi 85 I. = 90 ° / o 35 f 20th I.

Le A13 576

- 33-209825 / 11A4

Example G
LD ₁₀₀ -Test

Test animals: Sitophilus granarius
Solvent: acetone

2 parts by weight of active ingredient in 1,000 parts by volume of solvent recorded. The solution obtained in this way is diluted to the desired concentrations with further solvent.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. A filter paper with a diameter of about 9.5 cm is located on the bottom of the Petri dish. The petri dish remains Stand open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution

2
the amount of active ingredient per m of filter paper varies. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction is determined in %.

Active ingredients, active ingredient concentrations, test animals and results can be seen from the following table 7:

Le A 13 376 - 34 -

209825/1 144

JS

Tabel

/ Sitophilus granarius)

Active ingredient / = T ^CH 3 20th Active ingredient concentrations
tration of the solution
in $> Degree of destruction
in fo ^S J
Il / N-NH 0.2 '100 0.02 70 J = CJ -CH ₃ CN OCH ₃ ^{25 2} λ L
Il ^
0 NN-CH ₃ 0.2 0 (known) CN OCH, S.
(CH ₃ O) ₂ PO- NN-CH ₃ CN OCH,
NN-CH ₃ 0.2 100 (known) Γ * TiT ίΛΓ ¹ DD 0.02
0.002 100
100 NN-CH ₃ 0.2
0.02 100
100 (CH ₃ O) ₂ PO. 0.002 100 C ₂ H ₅ S 0.2
0.02
0.002 100
100
100 2 5 i 0.2 100 CH, S
• 2n.ii
> ° -
XC ₃ H ₇ O 0.02
0.002 100
100 S. - 35 - (CH ₃ O) ₂ PO. 9825 / 1UA Le A13 376

Port setting table

(LD-j _no -Test / Sitophilus granarius) Active ingredient concentration

Active ingredient CN OC ₀ Hc-
\ / / 2 5 tration of the solution
in general Degree of destruction
in ° / o S. 0.2 100 Il
ι C ¹ TT Πι "PO NN-GH ₃ 0.02 100 Γ \ "KT f \ Γ \ TT 0.002 80 S. 0.2 100 (C ₂ H ₅ O) ₂ PO NN-GH ₃ 0.02 100 W Ai V / w / * "5 Al ρ · 0.002 90 C ₂ H _r 0 S 0.2 100 ^ P-O NN-CH ₃ 0.02 100 C ₂ H ₅ 0.002 100

Le A 13 376 - 36 -

209825/1 UA

Production examples CN

s y

(CH ₃ O) ₂ P- ₅

A mixture of 50 g (0.3 mol) of 1-methyl-3-hydroxy-4-cyano-5-ethoxypyrazole and 45 g of potassium carbonate in 400 ecm of acetonitrile is mixed with 48 g (0.3 mol) of 0,0-dimethylthionophosphoric acid ester = Chloride added, the internal temperature initially being kept at room temperature. The reaction mixture warms up to 38 ^° C. after about 30 minutes. Stirring is continued overnight, poured into water, taken up with benzene and washed until the reaction is neutral. After drying, the solvent is stripped off and the residue is distilled off. There remain 70 g of the desired 0,0-dimethyl-0- (1-methyl-4-cyano ~ 5-ethoxypyrazol (3) yl) -thionophosphoric acid ester with the

25th
Refractive index η j. = T, 5074.

N S P ■

Ber. for C ₉ H ₁₄ N ₅ O ₄ PS (molecular weight 2'91): 14.4 # ;. $ 11.0; 10.6 <fo; Found: 14.3 fo-, 10.9 # '; 10.3 96 ...

The following connections are made in the same way: %

Constitution physical properties yield (refractive index, melting point) (^, of theory)

^{b Ί} '45 ⁰ C 85

^C 2 ^H 5j I 1 ^{51-52 0} C 89

Le A 13 376 - 37 -

209 8 2 5 / 1UA

constitution

Physical properties yield (refractive index, melting point) iio of theory)

(C ₂ H ₅ 0) gP-

= 1.4708

87

.OC ₃ H ₇ -I

(C ₂ H ₅ O) ₂ P-

= 1.4692

85

(CH ₃ O) ₂ PI

= 1.5031

76

IN

CH ,, S

OC ₃ H ₇ -I ^ CH,

^A 3

1-C ₃ H ₇ O
C ₂ II ₅ OS

C ₂ H ₅

-r ti ς-

= 1.5048

= 1.5079

= 1, 4937

80

--Il

C ₂ H ₅

(C ₂ H ₅ O) ₂ P-

cn, a

CH,

3 OCH,

.OCH

1-C ₃ H ₇ O

Le A13 376

= 1.5247

= 1.5081

Mp. 82 ^U C

- 38 209825/1144

88 87 69

Constitution Physical Properties Yield

- (refractive index, melting point) {jO the theory)

2 "Ί- C ■ n ² ^ = 1.4791 90

. 56 ⁰ G 83

The 1-methyl-3-hydroxy-4-cyano-5-ethoxypyrasol to be used as the starting material can be obtained, for example, as follows:

50 g (0.5 mol) of methyl cyanoacetate and 0.5 mol of sodium methylate are mixed with 68 g of S-methyl-O-ethyldithiocarbonic acid ester. The reaction that begins is slightly exothermic. The mixture is stirred further overnight at room temperature, rubbed with ether and the precipitate is filtered off with suction. After washing the latter with ether, the reaction product is dried on clay. 65 g (62 ^c / o of theory) of the desired compound are obtained

NC SNa I

GH ₃ OGO OC ₂ H ₅ ,

(0.3 mol) are mixed in 300 cc of methanol with 38 g of dimethyl sulfate by the now 63 g, the temperature of the mixture to 15 ⁰ C increases. After stirring for 3 hours, the batch is poured into water, the precipitate is filtered off with suction, dried and recrystallized from methanol. There are 39 g (65 Fe of theory) of the following compound

Le A 13 376 - 39 -

209825/1144

2U6Ü198

NC OC ₂ H ₅

obtained 64 ⁰ C of melting point. 20 g (0.1 mol) of this product are kept in 200 ecm of methanol together with 4.6 g of methylhydrazine at a temperature of 5 ms 7 ° C. for one hour. The mixture is then stirred overnight. The precipitated crystals are filtered off with suction and recrystallized from methanol. There remain behind 10 g (60 fo of theory) of the desired ™ 1-methyl-3-hydroxy-4-cyano-5-äthoxypyrazols a melting point of 206 ⁰ C.

The corresponding methoxy or iso-propoxy compound is produced in an analogous way:

Constitution pp. Yield

/ " ^D C_7 · (# äer theory)

C N J) CH _?

74

180 59

Le A 13 376 - 40 -

209825/1 U

Claims (3)

Claims
^ M pyrazolo- (thiono) -phosphorus (phosphonic) acid esters of the formula SOY ⁰ I ^0R R ₁ in which R and R .. stand for identical or different, straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, R _{1 is} also an alkoxy with 1 to 6 and Rg and R-z each represent an alkyl radical with 1 to Represents carbon atoms and Y represents an oxygen or sulfur atom. 2) Process for the preparation of pyrazolo (thiono) phosphorus = (Phosphonic) acid esters, characterized in that (thiono) phosphorus (phosphonic) acid ester halides of the formula RO Y P-HaI with i-alkyl ^ -hydroxy ^ -cyano ^ -alkyloxypyrazoles der Structure, IKL CE in the form of the corresponding salts or in the presence of Converts acid binders, where in the aforementioned formulas R, R ^, Rp, R · ^ and Y have the meaning given in claim 1, while Hai is a halogen, preferably Chlorine atom. Le A 13 376 - 41 - 209825/1 U4 3) insecticidal and acaricidal agents, characterized by a content of compounds according to claim 1. for the beating of insects and mites, thereby knitting, dairyman compounds according to claim 1 on diys sewn pests or their habitat. ) Use of compounds according to Claim 1 for combating insects and mites. ) Process for the preparation of insecticidal and acaricidal agents, characterized in that compounds according to Claim 1 mixes with extenders and / or surface-active agents. Le A13 376 - 42 - 209825/1 IU